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Synthetic routes and structures of [Rh(Hdmg){ClZn(C2H5OH)dmg}(PPh3)Cl], [Rh(Hdmg)2(PPh)2]+[Rh(Hdmg)2(Cl)2]- ·2CH3OH, and [Rh(Hdmg)2(PPh3)I] ·0.5C2H5OH complexes.
Autorzy
Rok wydania
2003
Czasopismo
Numer woluminu
22
Strony
3195-3203
DOI
10.1016/S0277-5387(03)00468-6
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Treatment of [Rh(Hdmg)2(PPh3)Cl] with zinc amalgam afforded a heterobimetallic compound [Rh(Hdmg)(ClZndmg)(PPh3)Cl] (1a) (Hdmg=monoanion of dimethylglyoxime). Crystallization of (1a) from a CHCl3/C2H5OH mixture led to the formation of [Rh(Hdmg){ClZn(C2H5OH)dmg}(PPh3)Cl] (1). The X-ray crystal structure of 1 revealed that the ethanol molecule was built into the complex molecule through the oxygen atom coordinated to the zinc cation and a hydrogen bond involving one of the chloride ligands. Reduction of [Rh(Hdmg)2(PPh3)Cl] with Zn/Hg, followed by treatment with a CHCl3/CH3OH mixture, gave the complex salt [Rh(Hdmg)2(PPh3)2]+[Rh(Hdmg)2(Cl)2]− · 2CH3OH (2). The X-ray structure of 2 showed crystals formed by cations [Rh(Hdmg)2(PPh3)2]+ and anions [Rh(Hdmg)2Cl2]−. The anion binds one CH3OH molecule through a hydrogen bond involving the adjacent oxime atom. Reduction of [Rh(Hdmg)2(PPh3)Cl] with zinc amalgam in the presence of CH3I led to the compound [Rh(Hdmg)2(PPh3)I] · 0.5C2H5OH (3), which was characterized by X-ray crystallography.The first instance of a bimetallic oximato compound containing Rh(III) and Zn(II) centres, 1, has been obtained and structurally determined in addition to two new rhodoximes, 2 and 3. It has been demonstrated that rhodium compounds with dioximato ligands can serve as suitable models for designing heteronuclear complexes.
Słowa kluczowe
Rhodium, Rhodoximes, Oximates, Spectral properties, Crystal structures
Adres publiczny
https://doi.org/10.1016/S0277-5387(03)00468-6
Strona internetowa wydawcy
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